Getting faster: low temperature copper-mediated SARA ATRP of methacrylates, acrylates, styrene and vinyl chloride in polar media using sulfolane/water mixtures

Abstract

Supplemental activator and reducing agent atom transfer radical polymerization (SARA ATRP) of acrylates, methacrylates, styrene and vinyl chloride was successfully performed in sulfolane/water mixtures using ppm amounts of soluble copper. The catalytic effect of the presence of water in the reaction mixtures resulted in a notable acceleration of the polymerization of the different monomers studied. The first-order kinetics with monomer conversion and the low dispersity values (Đ) of the polymers revealed the controlled features of the polymerization. As a proof-of-concept, an ABA block copolymer of poly(methyl acrylate)-b-poly(vinyl chloride)-b-poly(methyl acrylate) was prepared, confirming also the “living” character of the polymers. The results presented in this contribution extend the importance of sulfolane as an universal industrial solvent for the SARA ATRP of a broad range of monomer families by significantly enhancing the polymerization rate, due to the selective addition of water to the solvent mixture. The incorporation of small amounts of water in the solvent mixture has also allowed the use of FDA-approved sulfites as the SARA agent, which was not possible using pure sulfolane as the polymerization solvent.